4-nitro-2, 6-di(trifluoromethyl)-benzeneazo-nu-fluoroalkyl-nu-hydroxyalkylaniline dye compounds



Patented Apr. 29, 1952 4- NITRO-2,6- DI (TRIFLUOROMETHYL) BEN ZENEAZON-FLUOROALKYL-N-HYDROXY- ALKYLANILINE DYE COMPOUNDS Joseph B. Dickey, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y. a corporation of New Jersey No Drawing. Application April 1, 1949. Serial No. 85,044

7 Claims. (Cl. 260-2015) 1 This invention relates to new azo compounds and their application to the art of dyeing or coloring.

I have discovered that the azo compounds having the formula:

C Fa

l R NOg--N=N. N/ 4/ R1 Fa X wherein R represents a CHzCI-IFz, a CHzCFx, a CH2CH2CHF2 01 a --CH 2CF2CH3 group, R1 represents a b-hydroxyethyl group, a 'y-hydroxypropyl group or a fi,' -dihydroxypropyl group and X represents a hydrogen atom, a halogen atom having an atomic weight of from 19 to 80 or an alkyl hydrocarbon group having 1 to 2 carbon atoms are valuable dyes for coloring textile materials made of or containing a cellulose alkyl carboxylic acid ester having two to four carbon atoms in the acid groups thereof. They are particularly of use for the coloration of cellulose acetate textile materials. They-color the aforesaid textile materials orange shades which are slightly brownish from an aqueous suspension of the dye. The dyeings thus obtained possess very good fastness to light and gas.

It is an object of my invention-to provide new azo dye compounds. Another object is to provide a satisfactory process for the preparation of the new azo dye compounds of the invention. A further object is to provide dyed'cellulose alkylca-rboxylic acid ester textile materials which possess very good fastness to light and gas. A particular object is to provide new azo compounds which are especially of value for the dyeing of cellulose acetate textile materials.

By cellulose alkvl carboxylic acid esters having two to four carbon atoms in the acid groups thereof I mean to include, for example, both .hydrolyzed and unhydrolyzed cellulose .acetate cellulose propionate, cellulosebutyrate, cellulose acetate-propionate and cellulose acetate-butyrate.

The new azo dye compounds of my invention are prepared by dia-z'otizing *i-nitro-2,6-di--'(-trifiuoromethyl) aniline and coupling thediazonium compound obtained with ;a compoundhaving "the formula:

wherein R, R; and X have-the meaning-previously assigned to them. i

2 The following examples illustrate the azo compounds of my invention and their manner of prenatatie EXAMPLE 1 A. Preparation of nitrosyl sulfuric acid 500 cc. of sulfuric acid (95-96%? were placed in a 5-liter flask fitted with a stirrer and thermometer and then 76 grams of commercial sodium nitrite (90-95% pure) were added with vigorous stirring. The temperature of the reaction mixture rose to 70 .C'.-75 C. The reaction mixture was stirred and cooled to C.-14 C. Then 1200 cc. of acetic acid were added, with stirring, while maintaining the temperature of the reaction mixture below 20 C.

B. Diazotz'zation 274 grams of 4.-nitro- 2,6-di-(trifiuoromethyl)- aniline were added portionwise, with stirring, to the nitrosyl sulfuric acid prepared as described above and simultaneously 1 liter of cold acetic acid was added. Stirring was continued until the diazotization reaction which takes place was complete. Throughout the diazotization reaction a temperature of about 15 C. was maintained and this temperature was maintained during the coupling reaction described hereinafter.

C. Coupling grams of N-fifl-difiuoroethyl-N-fihydroXyethylaniline were dissolved in cc. of cold acetic acid and one tenth of the diazonium solution i prepared as described above was added with stirring. The coupling reaction which takes place was completed by adding sodium carbonate until the reaction mixture was neutral to Congo Red paper, i. e., until .the mineral acid (1. e. sulfuric acid) present was neutralized. A temperature of about 15C. was maintained throughout the coupling reaction. The dye compound formed by the coupling reaction was precipitated by the addition of water, recovered by filtration, washed well with water and dried. The dye compound thus obtained has the formula:

C'F: V V

I cmomon nes's' to-lig'ht and-gas.

EXAMPLE 2 23 grams of m-chloro-N-BJS-difiuoroethy1-N- B-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 3 21.4 grams of N-ABfi-trifluoroethyl-N-B-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

OHzCHzOH CH2CHF2 CHL'OHIOH CHzC F:

It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastnes-s to light and gas.

EXAMPLE 4 21 grams of m-methyl-N-ptp-difluoroethyl- N-[i-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example'l. The coupling reaction and recovery of the'dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

CHzCHaOH It colors cellulose acetate textile materials slightly brownish-orangeshades having excellent fastness to light and gas.

EXAMPLE 5 21 grams of N-p,p-difluoroethyl-N-y-hydroxypropylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

I CHn CHzCHaOH O H: C H F 2 It colors cellulose ace tate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 6 24' grams of m-methyl-N-pfi-difluoroethyl-N- 5, -dihydroxypropylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound f ormed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

CHzCHOHCHzOH I C H: C H F 2 F 3 C H3 It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 7 22.8 grams of m-methyl- N-msfl-trifluoroethyl- N-p-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery'of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

l CHaCHzOH It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAIVIPLE 8 21.4 grams of N-p o-difluoropropyl-N-B-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

OFs

. J) E: It colors cellulose acetate textile materials slightly brownish-orange shadeshaving excellent fastness to light and gas.

EXAMPLE 9 21 grams of N-mY-difiuoropropyl-N-p-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

CHzCHaOH CHgCFzCH:

CH2CH2OH CHzCH1CHF1 Fa It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

CHaCHOHCHiOH i 'CHgCHF F:

It colors cellulose acetate textile materials slightly brownish-orange shades having excellent tastness to light and gas;

EXAMPLE 11 22.8 grams of N -dfip-trifiuoroethyl N-w hy droxypropylaniline are coupled with one tenth ofa diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described'in Example 1. The dye compound obtained has the formula:

22.4 grams of m-ethyl-N-p,B difiuoroethyl-N- p-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovcry of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained has the formula:

It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 23.8 grams of m-ethyl-N-as-difiuoroethyl-N-'y-hydroxypropylaniline instead of m-ethyl N-B,Bdifluoroethyl-N fi-hydroxyethyk aniline in the example .just given, a dye compound is obtained which colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 13 21.3 grams of m-fluoro-N-fl,fi-difiuoroethyl N- fi-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example .1. l he dye'compound obtained has the formula:

CF: I

It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 27.6 grams of m-bromo-N-pp-difiuoroethyl-N-B-hydroxyethylaniline in place of m-fluoro-N-mc-difluoroethylN-fl hydroxyethylaniline in the example just given, a dye emnpound is obtained which colors-cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 14 24.8 grams of m-chloro-N-,8,B,p-trifiuoroethyl- N-p-hydroxyethylaniline are coupled with one tenth of a diazonium solution preparedas described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 29.3 grams of m-bromo-N-c,5,ptrifluoroethyl-N-/3-hydroxyethylaniline and 23.2 grams of m fluoro-N-B,;8,fil-trifluoroethyl-N-5- hydroxyethylaniline, respectively, in place of m-chloro N -fi,5,B-trifiuoroethyl e N-c-hydroxyethylaniline in the example just given, dye com-- pounds are obtained which color cellulose acetate textile materials slightly brownish-orange shades EXAMPLE 15 24.2 grams of m-ethyl-N-sfi,B-difiuoroethyl- N-p-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 27.2 grams of m-ethyl-N-B,B,/3- trifiuoroethyl N-my-dihydroxypropylaniline in place of m-ethyl-N-p,5,B-trifiuoroethyl-N-s-hydroxyethylaniline in the example just given, a dye compound which colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas is ob tained.

- EXAMPLE 16 24. grams of N-y,y-difluoropropyl-Nqfl dihydroxypropylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of thedye compound formed are carriedout exactly as described in Example 1. The dye compound obtained has the formula:

CFs

| CH2OHOHCH2OH It colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

Bythe use of 22.8 grams of N-y,' -difluoropropyl-N-' -hydroxypropylaniline in place of N-y,ydifiuoropropyl N 5;, hydroxypropylaniline in the example just given, a dye compound which colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas is obtained.

EXAMPLE 1'7 I 24.5 grams of m-chloro-N-w difiuoropropyl N-fi-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed are carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile .materials slightly .brownish orange shades having excellent fastness to light and gas.

By the use of 29 grams of m-bromo-N- m difluoropropyl-N-B-hydroxyethylaniline and 22.9 grams of m-fiuoro-N-' ,'y-difluoropropyl-N-f3- hydroxyethylaniline, respectively, instead of mchloro N 'y,'y difiuoropropyl N hydroxyethylaniline in the example just given, dye compounds are obtained which color cellulose acetate textile materials slightly brownishorange shades having excellent fastness to light and gas.

EXAMPLE 18 24.5 grams of m-chloro-N-p,,9-difluoropropyl- N-fi-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish orange shades having excellent fastness to light and gas.

By the use of 24.2 grams of m-fluoro-N-5,B- difluoropropyl N 'y hydroxypropylaniline and 31.9 grams of m-bromo-N-fi,B-difiuoropropyl N 5, dihydroxypropylaniline, respectively, instead of m-chloro-N-B,B-difiuoropropyl-N-li-hydroxyethylaniline in the example just given, dye compounds are obtained which color cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 19 22.4 grams of m-methyl-N-pm-difiuoropropyl- N-p-hydroxyethylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownishorange shades having excellent fastness to light and gas. By the use of 23.8 grams of m-ethyl-N-pfidifluoropropyl-N-B-hydroxyethylaniline instead of m-methyl-N-Bp-difiuoropropyl-N-c-hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 20 25.2 grams of m-ethyl-N-'y y-difluoropropyh N-y-hydroxypropylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownishorange shades having excellent fastness to light and gas.

By the use of 25.4 grams of m-methyl-N- 'y,'y difiuoropropyl N 1 ,7 dihydroxypropylaniline instead of m-ethyl-N-y,- -difluoropropyl-N-'y-hydroxypropylaniline, a dye compound which colors celluolse acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas is obtained.

EXAll/[PLE 21 22.4 grams of N-wy-difiuoropropyl-N-'y-hydroxypropylaniline are coupled with one tenth of a diazonium solution'prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 24 grams of N-'y,'- -difiuO1O propyl-N-Bq-dihydroxypropylaniline instead of N 7,7 difluoropropyl N 'y hydroxypropylaniline, a dye compound is obtained which colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 22 24 grams of N-pfi-difluoropropyl-N-p,'y-dihydroxypropylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 22.4 grams of N-fiJi-difiuoropropyl-N-'y-hydroxypropylaniline instead of N- 5 9 difiuoropropyl N B y dihydroxypropylaniline, an azo dye is obtained which colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 23 24.2 grams of m-methyl-N-p,B,B-trifluoroethyl N 'y hydroxypropylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 27.2 grams of m-ethyl-N-Bfifitrifiuoroethyl N 13, dihydroxypropylaniline in place of m-methyl-N-pfi,fl-trifluoroethyl-N- -hydroxypropylaniline, an azo dye is obtained which colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 24 27.9 grams of m-chloro-N-/3,13,p-trifluoroethyl- N-fl; -dihydropropylaniline are coupled with one tenth of a diazonium solution prepared as described in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 30.7 grams of m-bromo-N-fififitrifluoroethyl-N-v-hydroxypropylaniline and 24.6

grams of m-fluoro-N-,cfifi-trifluoroethyl-N-yhydroxypropylaniline, respectively, instead of mchloro- N -[3, 3,fl-trifluoroethyl-N-pgy-dihydropropylaniline, azo dyes. are obtained which color cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

EXAMPLE 25 24.4 grams of m-fiuoro-N-pfi-difluoroethyl-N- .v-dihydroxypropylaniline are coupled with one tenth of a diazonium, solution prepared as de;-

scribed in Example 1. The coupling reaction and recovery of the dye compound formed is carried out exactly as described in Example 1. The dye compound obtained colors cellulose acetate textile materials slightly brownish-orange shades having excellent fastness to light and gas.

By the use of 24.5 grams of m-chloro-N-c,;9-difluoroethyl-N-'y-hydroxypropylaniline and 30.5 grams of m-bromo-N-B,B-difluoroethyl-N-fi,'y-dihydroxypropylaniline, respectively, instead of mfluoro- N -;3,B-difluoroethyl-N-;B,'y-'dihydroxypropylaniline, azo dyes are obtained which color cellulose acetate textile materials slightly brown;- ish-orange shades having excellent fastness to light and gas.

The acetic acid used in Example 1 was commercial acetic acid. It is essentially glacial acetic acid. In order that the preparation of the azo compounds of my invention may beentirely clear, the preparation of the intermediate compounds used in their manuf'aoutre is disclosed hereinafter. Compounds having the formula:

were prepared by reacting a compound having the formula: 1 7

with ethylene oxide, BrCI-IzCI-IzCI-IzOI-I,

ClCHzCECI-IzOH is used, the hydrogen atom attached'to the nitrogen atom is replaced by a B-hydroxyethyl group. When BrCI-IzCI-IzCI-IzOI-I or C1CH2CH2CH2OH is used, the hydrogen atom is replaced by a 'y-hy droxypropyl group and when glycerol chlorohydrin is used, the hydrogen atom is replaced by a fi,'y-dihydroxypropy1 group. R, R1 and X have the meanings previously assigned to them. The

preparation of the above compounds will be apparent from the examples given hereinafter.

A. Preparation of N-c,cdifluoroethyZ-N-B hydrozcyethylanilz'ne B. Preparation of 1n-chZor0-N-B,5-;difluoroethyl N-fi-hydroxyethylaniline I 19.1 grams of N-B,fi-difiuoroethyl-m-chloroanie line and 5.06 grams of ethylene oxide were heated at 210 C. for 15 hours in a sealedxglass tube. Then the reaction mixture was cooled, removed from the tube and distilled under reduced pres sure (about 14 mm). 21.4 grams (91% of theory) of m-chloro-N-;9,,3-difluoroethyl-N-phydroxyethylaniline boiling at-180 01-182? C./14 mm. were obtained.

By the use of 17.5 grams of N-p,e difluoroethyl'- x or glycerol chlorohydrin. When ethylene oxide proximately 6 hours.

mfluoroanili'ne in place of N-p,c-difiuoroethylm-chloroaniline in the example just given, about hydroxyethylaniline boiling at 125 C.127 C./3 mm. are obtained.

C. Preparation of m-methyZ-N-p,;3-difluoroethyl- N-p-hydroxyethylaniline 51.5 grams of m-methyl-N-c,p-difluoroethylaniline,'15.8 grams of ethylene oxide and about 1500. of ethyl alcohol were sealed in a glass tube and heated, with shaking,'in an autoclave containing about 150 cc. of ethyl alcohol for 15 hours at 195 C. The reaction mixture was then cooled, removed from the tube and distilled under a reduced pressure of about 1 mm. 52.5 grams of m-methyl- N -B,,B-difluoroethyl- N -e-hydroxyethylaniline boiling at 112 (ll-118 C./about 1 mm. were obtained. The reaction product obtained as just described was distilled under a reduced pressure of about 1 mm. on a packed column 12 inches long. A smallforerun boiling at 121123 C./about 1 mm. was obtained and then-24grams boiling-at 123 C./about 1 mm. were collected separately. This fractionconsists of m-methyl-N-p,p-difluoroethyl-N-,B-hydroxyethylaniline in a high state of purity.

B. Preparation of N-cc-difluoroethyl-N- hydroxypropylanz'line (BrCHzCHzCHzOI-I) were added dropwise, with stirring, over a period of about 30 minutes and then the reaction mixture was heated, with stirring, to 140 C. for ap- The reaction mixture was distilled under'reduced pressure (1 to 2 mm.).

Analysis I Calculated Found 61. 5 61. a 7 0 6. l 6. 5 G. 2

E. Preparation of N-p,3-difluoroethyZ-N-e' -difluoropropylaniline 31.3 grams of"N-pfi-difluoroethylaniline and 20.2 grams of NaI-ICO; were placed in a 3-necked flask equipped with a thermometer and stirrer and heated to C.- C. with stirring. 26.4

grams of glycerol chlorohydrin were then added "dropwise and the reaction mixture was heated to C;- C. for 5-6 hours. Upon cooling, the reaction mixture was mixed with water (to remove NaCl, unreacted glycerol chlorohydrin, etc.) and the water layer was separated from the layer containing the desired product. This latter layer was then heated under reduced pressure (3 mm.) to 110 C. to remove unreacted materials. The residue (17.5 grams) consisted essentially of N-Bfi-difluoroethyl N -B/Y difiuoropropylaniline melting at 46 C.53 C.

F. Preparation of m-ethyl-N-p3,;s-difluoroethyl- N-fl,y-dihydromypropylaniline I -9.2 grams of N 5,19 difluoroethyl m ethylaniline, 6.5 grams of glycerol chlorohydrin and grams of Nal-ICOz were placed in a 3-necked flask equipped with a thermometer, stirrer and reflux condenser and heated, with stirring, for 5 hours at 150 C.155 C. in an oil bath. A vigorous reaction began at 145 C. giving 011" C02 and H20. Upon completion ofthe reaction, the reaction mixture was cooled and water was added to dissolve NaCl, unreacted glycerol chlorohydrin, etc. The reaction mixture was then filtered to remove any insoluble material and following this benzene was added to the filtrate. A water layer and a benzene layer formed and these two layers were separated from one another by means of a separatory funnel. The benzene layer was washed twice with water and then the benzene was removed from the benzene layer by distilling it under reduced pressure. The viscous brown material remaining after removal of the benzene was heated in an oil bath to 130 C. at 1 mm. pressure. 3 grams of low boiling material were removed. The viscous brown material remaining in the flask and consisting essentially of'm-ethyl- N 42,5 difluoroethyl N 13, dihydroxypropylaniline was bottled without further distilling.

G. Preparation of N-;8,p-difluoropropyl-N-s-hydromyethylaniline 17 grams of N-fip-difiuoropropylaniline, 5.2 grams of ethylene oxide and 5 cc. of ethyl alcohol were sealed in a glass tube and heated in a shaking autoclave for 95 hours at 190 C. The reaction mixture was then cooled, removed from the tube and distilled under reduced pressure (6 mm.) 18 grams of N-flfi-difiuoropropyl-N-B- hydroxyethylaniline boiling at 145 C.-148 C./6 mm. were obtained.

H. Preparation of m methyl N 'm difiuoropropyl-N-fl-hydrowyethylaniline grams of a fraction boiling at 130 C./1 mm. were collected. This latter fraction consisted of m methyl N 'y,'y difluoropropyl N B hydroxyethylaniline, the desired product.

Compounds having the formula:

can be prepared by reactin a suitable fluoroalkyl halide with a compound having the formula:

in the presence of an acid binding agent. R and X in the above formulas have the meaning previously assigned to them. Acid binding agents that can be used, include, for example, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.

I. Preparation of N 3,;8-diflaoroethy laniline 72.5 grams of 1,1-difluorq-2-bromoethane, 46.5 grams of aniline, 42 grams of sodium bicarbonate and 1 gram of sodium iodide were heated with shaking in an autoclave for 15 hours at C. The reaction mixture was cooled to room temperature, removed from the autoclave by washing with benzene (200 grams) and water, and the resulting mixture was filtered to remove a small amount of insoluble material. The benzene layer was separated from the water layer, washed with water and then distilled to remove the benzene and any remaining water. Upon distilling the residue through a 12" indented column (Claisen) under a reduced pressure of about 19 mm. 66 grams (84% of theory) of N-fip-difiuoroethylaniline boiling at 104 C.106 C./ 19 mm. were obtained.

J. Preparation of m-chimp-N pp-diflaoroethylaniline 72.5 grams of 1,1-difiuoro-2-bromoethane, 68.8 grams of m-chloroaniline, 42 grams of sodium bicarbonate and 1 gram of sodium iodide were heated ina shaking autoclave for 20 hours at about C. The reaction mixture was cooled to room temperature, removed from the autoclave by washing with benzene (200 grams) and water and the resulting mixture was filtered to remove a small amount of insoluble material. The benzene layer was separated from the water layer and then distilled to remove the benzene and any remaining water. Upon distilling the residue through a 12" indented column (Claisen) under a reduced pressure of about 16 mm., 81.5 grams (85% of theory) of m-chloro- N-/3,fi-difiuoroethylaniline boiling at 129 C.133 C./16 mm. were obtained.

By the use of 55.5 grams of m-fiuoroaniline in place of m-chloroam'line of the foregoing example, about 74 grams (84% of theory) of mfiuoro-N-Bfi-difiuoroethylaniline boiling at 118 C.-119 C./7 mm. are obtained.

K. Preparation of m-ethyZ-N-p,,8-diflaoroethyl aniline 24 grams of m-ethylaniline, 32 grams of 1,1-

- difiuoro-2-bromoethane, 19 grams of NaI-ICOs, 50

cc. of toluene and 1 gram of sodium iodide were .L. Preparation of m-m'ethgZ-N-vm-difl r i pylaniline 52.5 grams of 1,1-difiuoro-3-bromopropane (cHFzCHzCHzBr) 32.1 grams of m-toluidine and 27.7 grams of sodium bicarbonate were heated together in a suitable reaction vessel for 12 to 13 hours on a steam bath with stirring. Then the reaction mixture was cooled and 48 grams of a viscous liquid were recovered by decantation. The residue (principally NaBr) was washed with benzene and filtered. The viscous liquid and the benzene extract of the NaBr were combined and distilled to remove benzene. Then the residue remaining was fractionated under a reduced pressure of 27 mm. 33 grams of m-methyl-N- -y.'y-difluoropropylaniline which boils at 146 C;- 147" (1/27 mm. were obtained.

13 M. Preparation of m-methyZ-N-pp-dz'fluoroethylam'line 160 grams of m-toluidine, 218 grams of 1,1-difiuoro-2-bromoethane, 126 grams of Nal-ICOa and 3 grams of sodium iodide were heated, with shaking, in an autoclave for hours at 170 C.- 175 C. Upon cooling, the reaction mixture was washed out of the autoclave with toluene and water and then filtered to remove any insoluble material present. The oil layer was separated from the water layer and after washing with water the oil layer was heated to remove the toluene and any water remaining therein. The residue was then' distilled under a reduced pressure of 7 mm. to obtain 195 grams (76%-yie1d) of m-methyl-N-pp-difiuoroethylaniline which distilled over at 95 C.99 C./7 mm.

N. Preparation of N-p,p,,3-irifiuoroethylaniline 40 grams of 1,1,1-trifluoro-2-chloroethane and 64.6 grams of aniline were placed in a Carius tube cooled in an acetone-Dry Ice bath. The sealed tube was placed in a shaking autoclave and heated at 250 C.-225 C. for 30 hours. Upon cooling, the tube was opened and thecontents poured into a mixture of 420 cc. of water and 80 grams of hydrochloric acid (sp. gr. 1.18). The dilute acid completely dissolves the aniline, while the N-p.18,B-trifluoroethylaniline formed by the reaction and the reaction Icy-product diphenylamine are insoluble. The reaction mixture was extracted with two 50 gram portions of benzene. The two benzene extracts were combined, washed free of acid and then distilled. On distillation under a reduced pressure of 15 mm., 24.1 grams (40.6% of theory) of N -fl,B,B-trifluoroethylaniline boiling at 84 C.-85 C./15 mm. and having a refractive index of ND 1.4820 was obtained.

13.5 grams of N-p,5,B-trifluoroethylaniline. and 4.84 grams of ethylene oxide dissolved in 10 cc. of ethyl alcohol were placed in a Carius tube. The sealed tube was shaken in an autoclave for hours at 210 C.-220 C. Upon cooling, the tube was opened and the contents removed therefrom. Upon distillation under a reduced pressure of 15 mm., 16 grams of N-B,fl,fi-trifluoroethyl-N-;3-hydroxyethylaniline boiling at 102 C.-

103 C./15 mm. were obtained.

Similarly, the following compounds, for example, are obtained.

Compound Boiling Point B. Preparation of N-,B, 3-difluoropropylaniZine 15 mm). Several fractions were collected as shown hereinafter:

Fraction Boiling Point aniline. An analysis of the product is given hereinafter:

Calculated Found Per Cent Per Cent Any of the other coupling compounds used in the preparation of the azo compounds of my invention can be prepared by means of the pro: cedures just described.

Although 4-nitro-2,6-di- (trifiuoromethyl) -aniline is a known compound, its preparation from the known compound 2,6-di-(trifiuoromethyD- chlorobenzene is described hereinafter.

Q. Preparation of 4-nitro-2,6-di-(trifluoromethylbchlorobenzene v 50.5 grams of 2,6-di-(trifluoromethyl)-chlorobenzene were added with stirring to a mixture of '70 grams of 100% sulfuric acid and 14 grams of fuming sulfuric acid. Then a mixture of 28 grams of 100% sulfuric acid and 19.5 grams of fuming nitric acid (sp. gr. 1.49) were added slowly with stirring while keeping the temperature below 30 C. and the reaction mixture was stirred for 1 hour at room temperature. The reaction mix ture was heated to 90 C. and then slowly allowed to cool to C. C. and maintained at this temperature for 1 hour after which it was left to stand overnight at room temperature. Then the reaction mixture was poured over cracked ice and the product recovered by filtration. 40.5 grams of 4-nitro-2,6-di- (trifluoromethyl) -chloro benzene melting at 35 C.-36 C. were obtained.

R. Preparation of 4-m'tro-2,6-di-(triflaoromethyl) -aniline 30 grams of 4nitro-2,6-di-(trifluoromethyl)- chlorobenzene, 300 grams of absolute ethyl alcohol, 33 grams of ammonia and 0.5 gram of cuprous chloride were placed in an autoclave and heated to C.- C. for '7 hours. Upon cooling, the reaction mixture was removed from the not was much lighter in melting at C.-14'7 C. was obtained as a yellowish solid.

Analysis: Per cent N-calculated 10.2 N-found 10.1

On recrystallization from ethyl alcohol, the prodcolor and melted at 147 C.-l49. C. Theazo dye compounds .of myinventioncan be applied to the textile materialsindicated heral inbefore in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as Turkey red oil, sulfite cellulose solution, soap, or an oleyl glyceryl sulfate and the resulting paste is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.-55 C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to 80 C.90 C. and maintained at this point until dyeing is complete, usually one half hour to two hours. Upon completion of the dyeing operation the textile material is removed from the dyebath, washed with soap, rinsed well with water and dried.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, /3 to 3% (by weight) of that of the textile material although lesser or greater amounts of dye can be employed.

1,1-difluoro-3-bromopropane (CHFzCHzCHzBr) appears to be a new compound. It was prepared as described hereinafter.

S. Preparation of 1,1-difluoro-3-bromopropane 98 grams of 1,1,3-tribromopropane were placed in a 200 cc. round bottomed flask fitted with a still-head and a well-cooled receivin flask. 107 grams of dry mercuric fluoride were then added and the reaction flask was gently heated with a free flame until reaction began. The reaction was then allowed to proceed briskly but not too vigorously (by cooling in a bath of ice water or heating, as required) until all the reaction product had distilled over at about 85 C.- 100 C. The crude product was then steam-distilled, dried and fractionated. The main product was 1,1-difluoro-3-bromopropane, boiling point 92 C.-94 C. Using this procedure yields of 35-40% of pure 1,1-difluoro-3-brornopropane are obtained. A small amount of CHzFCHzCHzBI' was present in the residue.

1,1,3-tribromopropane (CHBmCHzCHzBr) likewise appears to be a new compound. It was prepared as described hereinafter.

T. Preparation of 1,1,3-trz'bromopropane 1000 grams of bromoform and 30 grams of benzoyl peroxide were placed in a 1100 cc. shaking autoclave and ethylene was passed into the autoclave until a pressure of 700 lbs. per sq. inch was reached. The reaction mixture was then heated at 85 C. for 15 hours following which it was cooled, removed from the autoclave and fractionated under reduced pressure. About 600 grams of 1,1,3-tribromopropane boiling at 105 C.-107 C./3O mm. were obtained. Using the procedure just described or generally similar procedures somewhat higher and somewhat lower yields were obtained. As high as 700 grams have been obtained. Also 100-150 grams of bromoform, 20-30 grams of a low boiling liquid andyarying amounts of higher boiling compounds are recovered.

The present application is a continuation-inpart of my prior applications Serial Nos. 631,468 and 631,469, filed November 28, 1945','now U. S. Patents 2,516,302 and 2,516,303, respectively, issued July 25, 1950.

I I claim: 1. The azo dye compounds having the formula:

C Fa

R NOz N= ON/ I Fa X .HzCHnOH (g CHzCHF:

Fa X

wherein X represents a halogen atom having an atomic weight of from 19 to 80.

. 3. The azo dye compounds having the formula:

CHQCHZOH I NOr- N=N N CHzCHFz Fa X wherein X represents an alkyl hydrocarbon group having 1 to 2 carbon atoms.

4. The azo dye compounds having the formula:

CFa

CHzCHzOH wherein X represents an alkyl hydrocarbon group having 1 to 2 carbon atoms.

5. The azo dye compound having the formula:

C Fa

NO: N=NON 6. The azo dye compound having the formula:

CHzCHROH CH -CHF Fa All 2 2 7. The azo dye compound having the formula:

CHzCHaOH CH2CHF2 v CFs CHzCHiOH NO: N=N-QN CHzCHFa JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,999,185 Engelmann Apr. 30, 1935 2,194,927 Daudt Mar. 26,1940 2,432,393 Dickey et a1 Dec. 9, 1947 2,516,302 Dickey July 25, 1950 2,516,303 Dickey July 25, 1950 

5. THE AZO DYE COMPOUND HAVING THE FORMULA: 